EP0403952B1 - An environmentally safe method of preparing a certain dialkylamine - Google Patents
An environmentally safe method of preparing a certain dialkylamine Download PDFInfo
- Publication number
- EP0403952B1 EP0403952B1 EP90111202A EP90111202A EP0403952B1 EP 0403952 B1 EP0403952 B1 EP 0403952B1 EP 90111202 A EP90111202 A EP 90111202A EP 90111202 A EP90111202 A EP 90111202A EP 0403952 B1 EP0403952 B1 EP 0403952B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- stage
- propyl
- accordance
- amine
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 42
- 125000005265 dialkylamine group Chemical group 0.000 title 1
- 239000002904 solvent Substances 0.000 claims abstract description 37
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 20
- CLFQSOIBYICELN-UHFFFAOYSA-N n-[2-(2,4,6-trichlorophenoxy)ethyl]propan-1-amine Chemical compound CCCNCCOC1=C(Cl)C=C(Cl)C=C1Cl CLFQSOIBYICELN-UHFFFAOYSA-N 0.000 claims abstract description 17
- VQUYNUJARXBNPK-UHFFFAOYSA-N 2-chloroethoxybenzene Chemical compound ClCCOC1=CC=CC=C1 VQUYNUJARXBNPK-UHFFFAOYSA-N 0.000 claims abstract description 16
- FBRGWNDXBBWEHK-UHFFFAOYSA-N n-(2-phenoxyethyl)propan-1-amine Chemical compound CCCNCCOC1=CC=CC=C1 FBRGWNDXBBWEHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 tetra-alkyl ammonium halide Chemical class 0.000 claims abstract description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 14
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229960005323 phenoxyethanol Drugs 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 5
- PRDUHXPVDHDGKN-UHFFFAOYSA-N tetrachloromethane;hydrate Chemical compound O.ClC(Cl)(Cl)Cl PRDUHXPVDHDGKN-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 3
- 125000005207 tetraalkylammonium group Chemical group 0.000 claims 3
- 235000019270 ammonium chloride Nutrition 0.000 claims 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 239000006227 byproduct Substances 0.000 description 8
- LINPIYWFGCPVIE-UHFFFAOYSA-N 2,4,6-trichlorophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1Cl LINPIYWFGCPVIE-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000005820 Prochloraz Substances 0.000 description 6
- TVLSRXXIMLFWEO-UHFFFAOYSA-N prochloraz Chemical compound C1=CN=CN1C(=O)N(CCC)CCOC1=C(Cl)C=C(Cl)C=C1Cl TVLSRXXIMLFWEO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- XIKACWWOANXRDC-UHFFFAOYSA-N CC(CC(C1)Cl)C(C)C1Cl Chemical compound CC(CC(C1)Cl)C(C)C1Cl XIKACWWOANXRDC-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
Definitions
- the present invention concerns the improved, environmentally safe process for preparing N-n-propyl-N-2-(2,4,6-trichlorophenoxy)-ethyl amine and its use as an intermediate in the preparation of the fungicide Prochloraz.
- EP 243,038 describes a process of preparing 2,4,6-trichlorophenol involving the slow controlled chlorination of phenol in the presence of a catalyst which is alleged to diminish the formation of the chlorinated by-products.
- EP 299,892 describes the chlorination of a chlorophenol using a different type of catalyst.
- N-n-propyl-N-2-(2,4,6-trichlorophenoxy)-ethyl amine may be prepared comprising the steps of:
- the reaction process is generally illustrated below on a batch-wise basis: -
- the temperature of reaction of Stage I may range from 0°C to 80°C, but is preferably in the range of from 10°C to 50°C.
- equimolar amounts of thionyl chloride may be used. However, an excess of up to 20% is preferred to ensure complete reaction.
- This reaction may be carried out with or without a solvent. If a solvent is used, halogenated hydrocarbons such as chloroform, dichloromethane and carbon tetrachloride are preferred, with dichloromethane being most preferred.
- the alkyl group of the tetra-alkyl ammonium halide may be chosen from the group consisting of straight or branched alkyl groups having from 1 to 16 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, heptyl, decyl and the like, cyclic alkyl groups such as cyclopentyl, cyclo-hexyl, cycloheptyl, cyclodecyl and the like and benzyl.
- Preferred alkyl groups are straight chain alkyl groups having from 1 to 8 carbon atoms and benzyl. Most preferred are methyl and benzyl, with the preferred halide as chloride. An especially preferred catalyst is benzyl trimethyl ammonium chloride.
- the tetra-alkyl ammonium halide is used in a concentration of 0.5% to 10%, preferably 3%, based on the 2-phenoxy-ethanol.
- the temperature of reaction of Stage II may range from 50°C to 150°C, but is preferably in the range of from 100°C to 110°C.
- the process of Stage II may be carried out with equimolar amounts of reactants. However, an excess of n-propyl amine is usually used to ensure completion of the reaction. While an excess of 100% to 300% can be used, it is more economical to run the reaction with the excess of about 20% amine.
- the process of Stage II may be run without the use of a solvent. However, then a very large excess of amine is required, which increases the work and makes the reaction uneconomical. It is, therefore, preferred to run Stage II in a solvent.
- Solvents such as ethanol, dimethyl formamide, acetonitrile and a mixture of ethanol-water were found suitable. Preferred solvents are ethanol or ethanol-water, with an ethanol-water mixture most preferred. The ratio of ethanol to water may be 1:1.6 to 1.6:1 and most preferred 1.3 to 1 by volume.
- the temperature of reaction of Stage III may range from 0°C to 80°C, but is preferably in the range of from 25°C to 40°C. However, the specific preferred temperature depends also on the type of solvent used.
- This stage may be run in the presence of a suitable solvent, such as chloroform, dichloromethane, carbon tetrachloride, carbon tetrachloride-water and acetic acid.
- a suitable solvent such as chloroform, dichloromethane, carbon tetrachloride, carbon tetrachloride-water and acetic acid.
- Preferred solvents are carbon tetrachloride-water and acetic acid, with acetic acid the most preferred solvent.
- the ratio of urea to N-n-propyl-N-2-phenoxyethyl amine ranges from 1:5 to 1:50, preferably 1:7 to 1:20, by weight.
- the final amine product can be isolated as a mineral acid salt, preferably as the hydrochloride acid audition salt, which forms nice white crystals which are easily handled.
- the free amine may he isolated by treating the hydrochloride salt with a base such as, for example, aqueous sodium carbonate to neutralize to pH 7, separating the phases and distill the organic layer to yield an oil boiling at 112°C-114°C at 0.2 mm Hg.
- the present invention affords a process for preparing N-n-propyl-N-2-(2,4,6-trichlorophenoxy)-ethyl amine in high yield, without having to handle the highly toxic 2,4,6-trichlorophenol and ethylene dibromide.
- the process of the instant invention is of note in that it affords high yields of the N-n-propyl-N-2-(2,4,6-trichlorophenoxy)-ethyl amine whereby the trichlorophenoxy group is formed at as late a stage as possible to avoid any possible decomposition of the trichlorophenoxy moiety of this group to form undesirable chlorinated by-products during reaction.
- the amine product may be reacted with phosgene and subsequently with imidazole according to GB 1,469,772 to afford Prochloraz, having essentially no detectable amount undesirable chlorinated by-products.
- Example 2 The same exact process of Example 1 was repeated without the use of solvent, where the only other difference was, that it was not necessary to remove any solvent after the washings. This afforded a similar yield of 2-phenoxyethyl chloride having the same purity.
- Example 4 The process of Example 4 was followed, but only 20 g of N-n-propyl-2-phenoxyethyl amine was reacted in 150 ml of acetic acid as solvent, using 3 g urea. Chlorination for 3.5 hours at a temperature of 35°C to 40°C afford a product in 85% yield having a purity of 92%.
- Example 5 The process of Example 5 was followed, but the chlorine gas was added over 2.5 hours at a temperature of 55°C to afford a product An 81% yield, having a purity of 93%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Saccharide Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IL90704 | 1989-06-21 | ||
| IL9070489A IL90704A (en) | 1989-06-21 | 1989-06-21 | Method for the preparation of N-N-) 2,4,6-trichlorophenoxy (environmentally reliable ethylene) |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0403952A2 EP0403952A2 (en) | 1990-12-27 |
| EP0403952A3 EP0403952A3 (en) | 1992-02-12 |
| EP0403952B1 true EP0403952B1 (en) | 1994-08-31 |
Family
ID=11060075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90111202A Expired - Lifetime EP0403952B1 (en) | 1989-06-21 | 1990-06-13 | An environmentally safe method of preparing a certain dialkylamine |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5093526A (hu) |
| EP (1) | EP0403952B1 (hu) |
| AT (1) | ATE110710T1 (hu) |
| DE (1) | DE69011977T2 (hu) |
| HU (2) | HU207709B (hu) |
| IL (1) | IL90704A (hu) |
| ZA (1) | ZA904573B (hu) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL106118A (en) * | 1993-06-24 | 1997-08-14 | Agan Chemical Manufacturers | Process for preparing n-alkyl-3,4-dialkyl- 2,6-dinitro- anilines and intermediates thereof |
| SE9704834D0 (sv) * | 1997-12-22 | 1997-12-22 | Astra Ab | New process |
| CN100340550C (zh) * | 2005-09-16 | 2007-10-03 | 华南师范大学 | 咪酰胺的制备方法 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1469772A (en) * | 1973-06-21 | 1977-04-06 | Boots Co Ltd | Fungicidal imidazole derivatives |
| US4504484A (en) * | 1982-11-04 | 1985-03-12 | Chevron Research Company | Certain N,N-di-substituted-pyridine carboxamides, fungicidal compositions and fungicidal method of use |
| GB8609904D0 (en) * | 1986-04-23 | 1986-05-29 | Fbc Ltd | Preparation of metal phenates |
| GB8714920D0 (en) * | 1987-06-25 | 1987-07-29 | Shell Int Research | Thiazole derivatives |
-
1989
- 1989-06-21 IL IL9070489A patent/IL90704A/en not_active IP Right Cessation
-
1990
- 1990-06-13 AT AT90111202T patent/ATE110710T1/de not_active IP Right Cessation
- 1990-06-13 DE DE69011977T patent/DE69011977T2/de not_active Expired - Fee Related
- 1990-06-13 ZA ZA904573A patent/ZA904573B/xx unknown
- 1990-06-13 HU HU903824A patent/HU207709B/hu not_active IP Right Cessation
- 1990-06-13 EP EP90111202A patent/EP0403952B1/en not_active Expired - Lifetime
- 1990-06-13 HU HU923863A patent/HU207984B/hu not_active IP Right Cessation
- 1990-06-14 US US07/537,972 patent/US5093526A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0403952A2 (en) | 1990-12-27 |
| HU903824D0 (en) | 1990-11-28 |
| HUT53864A (en) | 1990-12-28 |
| US5093526A (en) | 1992-03-03 |
| IL90704A0 (en) | 1990-01-18 |
| ZA904573B (en) | 1992-01-29 |
| HU207709B (en) | 1993-05-28 |
| ATE110710T1 (de) | 1994-09-15 |
| DE69011977T2 (de) | 1995-03-30 |
| HU9203863D0 (en) | 1993-03-29 |
| HU207984B (en) | 1993-07-28 |
| EP0403952A3 (en) | 1992-02-12 |
| IL90704A (en) | 1994-10-07 |
| DE69011977D1 (de) | 1994-10-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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